Can-Cheng Guo

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Name: 郭灿城; Guo, CanCheng

Organization: Hunan University , China

Department: College of Chemistry and Chemical Engineering

Title: Professor(PhD)

TOPICS

Inorganic Chemistry

Porphyrin

Chemicals
References

Transition-Metal-Free Oxidative Decarboxylative Cross Coupling of α,β-Unsaturated Carboxylic Acids with Cyclic Ethers under Air Conditions: Mild Synthesis of α-Oxyalkyl Ketones

Co-reporter:Peng-Yi Ji, Yu-Feng Liu, Jing-Wen Xu, Wei-Ping Luo, Qiang Liu, and Can-Cheng Guo

The Journal of Organic Chemistry March 17, 2017 Volume 82(Issue 6) pp:2965-2965

Publication Date(Web):February 22, 2017

DOI:10.1021/acs.joc.6b02993

A novel K2S2O8-promoted decarboxylative cross coupling of α,β-unsaturated carboxylic acids with cyclic ethers was developed under aerobic conditions. The present protocol, which includes C–C and C═O bond formation in one step through addition, oxidation, and decarboxylation processes, leads to the desired ketone products in moderate to excellent yields. In addition, mechanism studies showed that the transformation process undergoes a radical pathway via a direct activation of the α-sp3 C–H bond of oxygen of the cyclic ether.

Transition Metal-Free α-Csp3-H Methylenation of Ketones to Form C═C Bond Using Dimethyl Sulfoxide as Carbon Source

Co-reporter:Yu-Feng Liu, Peng-Yi Ji, Jing-Wen Xu, Yu-Qun Hu, Qiang Liu, Wei-Ping Luo, and Can-Cheng Guo

The Journal of Organic Chemistry July 21, 2017 Volume 82(Issue 14) pp:7159-7159

Publication Date(Web):June 26, 2017

DOI:10.1021/acs.joc.7b00619

A direct α-Csp3-H methylenation of arylketones to form C═C bond using dimethyl sulfoxide as one-carbon source is achieved under transition metal-free reaction condition. Various aryl ketone derivatives react readily with DMSO, producing the α,β-unsaturated carbonyl compounds in yields of 42 to 90%. This method features a transition metal-free reaction condition, wide substrate scope and using DMSO as novel one-carbon source to form C═C bond, thus providing an efficient and expeditious approach to an important class of α,β-unsaturated carbonyl compounds. Based on the preliminary experiments, a plausible mechanism of this transformation is disclosed.

Copper(I)-Catalyzed α-Acryloyloxylation of Ketones with α,β-Unsaturated Carboxylic Acids To Form α-Acryloyloxy Ketones

Co-reporter:Jing-Wen Xu;Peng-Yi Ji;Yu-Feng Liu;Wei-Ping Luo;Qiang Liu

European Journal of Organic Chemistry 2017 Volume 2017(Issue 3) pp:734-740

Publication Date(Web):2017/01/18

DOI:10.1002/ejoc.201601346

An efficient method for the α-C–H acryloyloxylation of ketones with α,β-unsaturated carboxylic acids was developed, using copper(I) as a catalyst. The most concise approach to form α-acryloyloxy ketones is through direct oxidative coupling at the α-C(sp3)–H position of ketones. This method gives the products in high yields, and has a wide substrate scope in terms of both ketones and unsaturated carboxylic acids. A copper(I)-catalyzed reaction mechanism is proposed based on the results of control experiments.

Transition metal-free C(sp3)–H bond coupling among three methyl groups

Co-reporter:Yufeng Liu;Xi Zhan;Pengyi Ji;Jingwen Xu;Qiang Liu;Weiping Luo;Tieqiao Chen;Cancheng Guo

Chemical Communications 2017 vol. 53(Issue 38) pp:5346-5349

Publication Date(Web):2017/05/09

DOI:10.1039/C7CC01309D

A coupling of multiple C(sp3)–H bonds of the methyl group in methyl ketones with dimethyl sulfoxide is developed. This coupling allows the direct C(sp3)–H bond coupling among three methyl groups and affords one C–C bond and one CC bond under transition metal-free conditions. The value-added cyclized 3-methylthiomethyl chroman-4-ones can be synthesized through this method. A plausible mechanism is proposed.

Copper porphyrin-catalyzed aerobic oxidative coupling of terminal alkynes with high TON

Co-reporter:Wen-Bing Sheng, Tie-Qiao Chen, Ming-Zhong Zhang, Mi Tian, Guo-Fang Jiang, Can-Cheng Guo

Tetrahedron Letters 2016 Volume 57(Issue 15) pp:1641-1643

Publication Date(Web):13 April 2016

DOI:10.1016/j.tetlet.2016.02.075

•UV–Vis spectra are carried out to detect the efficient intermediate Cu(III)-porphyrin.•Copper-porphyrin is an effective catalyst for the cross-coupling of terminal alkynes with excellent selectivity.•This reaction features high TON (up to 950) in homo-coupling of terminal alkynes with functional groups.Copper porphyrin-catalyzed Glaser–Hay-type couplings of terminal alkynes generating 1,3-diynes are described. This reaction features high TON (up to 950) and is complete in an hour, providing a facile, clean, and efficient protocol to access various 1,3-diynes including those with functional groups under mild reaction conditions. This transformation would take place via a radical process.

Direct synthesis of nitriles from cleavage of CC double bond with nitrite as the nitrogen source and oxidant

Co-reporter:Qiang Liu, Bao Fang, Xiaohui Bai, Yuan Liu, Yao Wu, Guiming Xu, Cancheng Guo

Tetrahedron Letters 2016 Volume 57(Issue 24) pp:2620-2623

Publication Date(Web):15 June 2016

DOI:10.1016/j.tetlet.2016.04.108

•A novel synthesis of aromatic nitriles from aromatic olefins.•Using cheap and widely available NaNO2 as the oxidant and nitrogen source.•The reaction proceeds smoothly under mild conditions in good to excellent yields.•Relative good functional group tolerance.•A new oxidative nitrogenation mechanism was proposed.The transformation of the CC bond of olefin to nitriles has been developed, using easily available NaNO2 as both the nitrogen source and oxidant. Several aryl, heterocyclic nitriles with various substituting groups could be successfully prepared in good to high yields. Based upon experimental observations, a possible reaction mechanism is proposed.

K2S2O8-mediated nitration of alkenes with NaNO2 and 2,2,6,6-tetramethylpiperidine-1-oxyl: stereoselective synthesis of (E)-nitroalkenes

Co-reporter:An Zhao, Qing Jiang, Jing Jia, Bin Xu, Yufeng Liu, Mingzhong Zhang, Qiang Liu, Weiping Luo, Cancheng Guo

Tetrahedron Letters 2016 Volume 57(Issue 1) pp:80-84

Publication Date(Web):6 January 2016

DOI:10.1016/j.tetlet.2015.11.064

A transition-metal-free nitration of alkenes with NaNO2 in the presence of K2S2O8 and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) is developed. The transformation exhibits a broad substrate scope and good functional group tolerance, thus providing a new and expedient protocol for stereoselective synthesis of (E)-nitroalkenes with moderate to good yields. Moreover, the nitration processes of (E)- and (Z)-stilbene are also studied: even though the proportion of substrates is different, the E/Z ratio of the products is basically the same. Based upon experimental observations, a possible reaction mechanism is proposed.

Transition-Metal-Free TBAI-Facilitated Addition–Cyclization of N-Methyl-N-arylacrylamides with Arylaldehydes or Benzenesulfonohydrazides: Access to Carbonyl- and Sulfone-Containing N-Methyloxindoles

Co-reporter:Peng-Yi Ji, Ming-Zhong Zhang, Jing-Wen Xu, Yu-Feng Liu, and Can-Cheng Guo

The Journal of Organic Chemistry 2016 Volume 81(Issue 12) pp:5181-5189

Publication Date(Web):May 27, 2016

DOI:10.1021/acs.joc.6b00773

A highly efficient addition–cyclization of N-methyl-N-arylacrylamides with arylaldehydes or benzenesulfonohydrazides was developed using a catalytic amount of the quaternary ammonium salt (TBAI) under metal-free conditions, leading to the carbonyl- and sulfone-containing oxindoles. Compared to previous methods, which require excessive amounts of explosive organic peroxides and precious or toxic metal reagents, the present protocol, which gave access to 3,3-disubstituted oxindoles, is a safe and green approach, resulting in the formation of various useful carbonyl- and sulfone-containing oxindoles in yields of 40–94%.

Measurement and Correlation for Solubilities of Adipic Acid in Acetic Acid + ε-Caprolactone Mixtures and Cyclohexanone + ε-Caprolactone Mixtures

Co-reporter:Weiping Luo; Dong Ruan; Dawei Liu; Kaili Xie; Xiuqing Li; Wei Deng;Cancheng Guo

Journal of Chemical & Engineering Data 2016 Volume 61(Issue 7) pp:2474-2480

Publication Date(Web):June 3, 2016

DOI:10.1021/acs.jced.6b00177

The solubilities of adipic acid in acetic acid + ε-caprolactone mixtures and in cyclohexanone + ε-caprolactone mixtures were measured by using the method of dynamic laser under atmospheric pressure. The experimental temperature ranged from 305.55 to 343.15 K, and the mass fraction of ε-caprolactone in the solvent mixtures ranged from 0.100 to 1.000, respectively. It was found that with the increasing of mass fraction of ε-caprolactone in solvent mixtures (0.100 to 1.000), the measured solubilities of adipic acid in acetic acid + ε-caprolactone mixtures decreased at the same temperature. However, in cyclohexanone + ε-caprolactone mixtures, the solubility showed an opposite trend with the increasing of mass fraction of ε-caprolactone in solvent mixtures. The experimental data were correlated by the modified NRTL activity coefficient model, and the values of the solubility calculated showed good agreement with the experimental observations.

Copper-catalyzed aerobic conversion of the CO bond of ketones to a CN bond using ammonium salts as the nitrogen source

Co-reporter:Bin Xu, Qing Jiang, An Zhao, Jing Jia, Qiang Liu, Weiping Luo and Cancheng Guo

Chemical Communications 2015 vol. 51(Issue 56) pp:11264-11267

Publication Date(Web):04 Jun 2015

DOI:10.1039/C5CC02578H

The conversion of the CO bond of ketones to a CN bond is described. This conversion is catalyzed by copper salts with ammonium salts as the nitrogen source in the presence of molecular oxygen. A wide variety of ketones can be converted into the corresponding compounds containing a CN bond. Based on the preliminary experiments, a plausible mechanism of this transformation is disclosed.

Potassium tert-Butoxide-Mediated Amine Acyl Exchange Reaction of N,N-Disubstituted Formamides with Aromatic Carbonyl Derivatives via Sequential CN Bond Cleavage/Formation: an Approach to Aromatic Amides

Co-reporter:Ming-Zhong Zhang;Qing-Hu Guo;Wen-Bing Sheng

Advanced Synthesis & Catalysis 2015 Volume 357( Issue 13) pp:2855-2861

Publication Date(Web):

DOI:10.1002/adsc.201500551

Metal-free direct cyanoisopropylation/arylation of N-arylacrylamides or N-alkyl-N-(arylsulfonyl)acrylamides with AIBN: a simple and mild approach to cyano-containing oxindoles

Co-reporter:Mingzhong Zhang, Wenbing Sheng, Pengyi Ji, Yufeng Liu and Cancheng Guo

RSC Advances 2015 vol. 5(Issue 70) pp:56438-56443

Publication Date(Web):17 Jun 2015

DOI:10.1039/C5RA10084D

A simple and metal-free direct cyanoisopropylation/arylation of N-arylacrylamides or N-alkyl-N-(arylsulfonyl)acrylamides with AIBN has been developed with cheap and readily available CH3NO2 as both the solvent and the oxidant. This reaction provides an efficient approach to cyano-containing oxindoles, which are highly valued synthetic intermediates of biologically active molecules. A series of N-alkyl-N-(arylsulfonyl)acrylamide substrates could be converted into the corresponding oxindoles in good yields and with excellent chemoselectivity via one-pot cyanoisopropylation/aryl migration/desulfonylation and C(sp2)-N bond formation. In contrast to previous reports, the mild conditions together with lack of a need for any metal catalysts and additional oxidants make this protocol very easy to handle and practical.

Iron-Facilitated Oxidative Radical Decarboxylative Cross-Coupling between α-Oxocarboxylic Acids and Acrylic Acids: An Approach to α,β-Unsaturated Carbonyls

Co-reporter:Qing Jiang, Jing Jia, Bin Xu, An Zhao, and Can-Cheng Guo

The Journal of Organic Chemistry 2015 Volume 80(Issue 7) pp:3586-3596

Publication Date(Web):March 10, 2015

DOI:10.1021/acs.joc.5b00267

The first Fe-facilitated decarboxylative cross-coupling reaction between α-oxocarboxylic acids and acrylic acids in aqueous solution has been developed. This transformation is characterized by its wide substrate scope and good functional group compatibility utilizing inexpensive and easily accessible reagents, thus providing an efficient and expeditious approach to an important class of α,β-unsaturated carbonyls frequently found in bioactive compounds. The synthetic potential of the coupled products is also demonstrated in subsequent functionalization reactions. Preliminary mechanism studies suggest that a free radical pathway is involved in this process: the generation of an acyl radical from α-oxocarboxylic acid via the excision of carbon dioxide followed by the addition of an acyl radical to the α-position of the double bond in acrylic acid then delivers the α,β-unsaturated carbonyl adduct through the extrusion of another carbon dioxide.

Transition-Metal-Free Synthesis of Carbonyl-Containing Oxindoles from N-Arylacrylamides and α-Diketones via TBHP- or Oxone-Mediated Oxidative Cleavage of C(sp2)–C(sp2) Bonds

Co-reporter:Ming-Zhong Zhang, Peng-Yi Ji, Yu-Feng Liu, and Can-Cheng Guo

The Journal of Organic Chemistry 2015 Volume 80(Issue 21) pp:10777-10786

Publication Date(Web):October 21, 2015

DOI:10.1021/acs.joc.5b01977

Carbonyl-containing oxindoles can be prepared from N-arylacrylamides and α-diketones by TBHP- or oxone (KHSO5)-mediated C(sp2)–C(sp2) bond cleavage and new C(sp2)–C(sp3) bond formation. This methodology is characterized by its simple and transition-metal-free conditions and good functional group compatibility utilizing inexpensive and readily available reagents, thus providing a practical and efficient approach to an important class of 3-(2-oxoethyl)indolin-2-ones which are highly valued synthetic intermediates of biologically active molecules. In this transformation, alkylcarbonyl-containing oxindoles were obtained in majority when N-arylacrylamides reacted with asymmetric aliphatic/aromatic α-diketones. On the basis of the preliminary experiments, a plausible mechanism of this transformation is disclosed.

Iodine(III)-Mediated C–H Alkoxylation of Aniline Derivatives with Alcohols under Metal-Free Conditions

Co-reporter:Qing Jiang, Jing-Yu Wang, and Cancheng Guo

The Journal of Organic Chemistry 2014 Volume 79(Issue 18) pp:8768-8773

Publication Date(Web):August 25, 2014

DOI:10.1021/jo501601u

The development of a novel intermolecular oxidative C–H alkoxylation of aniline derivatives is described under metal-free conditions with high reaction rates at ambient temperature. In the presence of an I(III) oxidant, a range of aldehydes, anilines, and alcohol substrates undergo three-component coupling to produce synthetically useful alkoxyl-substituted N-arylimines. The preliminary mechanism investigations revealed that the transformation proceeds via imines as intermediates.

Metal-Free Synthesis of Oxindoles via (NH4)2S2O8-Mediated Halocarbocyclization of Alkenes in Water

Co-reporter:Ming-Zhong Zhang, Wen-Bing Sheng, Qing Jiang, Mi Tian, Yong Yin, and Can-Cheng Guo

The Journal of Organic Chemistry 2014 Volume 79(Issue 22) pp:10829-10836

Publication Date(Web):October 24, 2014

DOI:10.1021/jo501741w

A metal-free synthesis of oxindoles was achieved through the (NH4)2S2O8-mediated halocarbocyclization of alkenes. This protocol provides a practical and environmentally benign method for the construction of halo-containing oxindoles in water. The advantages of this reaction are its good functional group tolerance and mild reaction conditions. On the basis of experimental observations, a plausible reaction mechanism is proposed.

Copper-Catalyzed Aerobic Decarboxylative Sulfonylation of Cinnamic Acids with Sodium Sulfinates: Stereospecific Synthesis of (E)-Alkenyl Sulfones

Co-reporter:Qing Jiang, Bin Xu, Jing Jia, An Zhao, Yu-Rou Zhao, Ying-Ying Li, Na-Na He, and Can-Cheng Guo

The Journal of Organic Chemistry 2014 Volume 79(Issue 16) pp:7372-7379

Publication Date(Web):July 15, 2014

DOI:10.1021/jo5010845

A copper-catalyzed aerobic decarboxylative sulfonylation of alkenyl carboxylic acids with sodium sulfinates is developed. This study offers a new and expedient strategy for stereoselective synthesis of (E)-alkenyl sulfones that are widely present in biologically active natural products and therapeutic agents. Moreover, the transformation is proposed to proceed via a radical process and exhibits a broad substrate scope and good functional group tolerance.

Transition-Metal-Free Oxidative α-C–H Amination of Ketones via a Radical Mechanism: Mild Synthesis of α-Amino Ketones

Co-reporter:Qing Jiang, Bin Xu, An Zhao, Jing Jia, Tian Liu, and Cancheng Guo

The Journal of Organic Chemistry 2014 Volume 79(Issue 18) pp:8750-8756

Publication Date(Web):August 25, 2014

DOI:10.1021/jo5015855

A transition-metal-free direct α-C–H amination of ketones has been developed using commercially available ammonium iodide as the catalyst and sodium percarbonate as the co-oxidant. A wide range of ketone ((hetero)aromatic or nonaromatic ketones) and amine (primary/secondary amines, anilines, or amides) substrates undergo cross-coupling to generate synthetically useful α-amino ketones. The mechanistic studies indicated that a radical pathway might be involved in the reaction process. The utility of the method is highlighted through a concise one-step synthesis of the pharmaceutical agent amfepramone.

PIFA-Mediated Esterification Reaction of Alkynes with Alcohols via Oxidative Cleavage of Carbon Triple Bonds

Co-reporter:Qing Jiang, An Zhao, Bin Xu, Jing Jia, Xin Liu, and Cancheng Guo

The Journal of Organic Chemistry 2014 Volume 79(Issue 6) pp:2709-2715

Publication Date(Web):March 6, 2014

DOI:10.1021/jo5003517

A metal-free esterification of alkynes via C≡C triple bond cleavage has been developed. In the presence of phenyliodine bis(trifluoroacetate), a diverse range of alkyne and alcohol substrates undergoes triple bond cleavage to produce carboxylic ester motifs in moderate to good yields. The transformation is proposed to proceed via hydroxyethanones and ethanediones as intermediates on the basis of mechanistic studies and exhibits a broad substrate scope and good functional group tolerance.

Study on the synthesis and structureeffect relationship of multi-aryl imidazoles with their fluorescence properties

Co-reporter:Mi Tian;Chao Wang;LiGong Wang;Kai Luo;An Zhao ;CanCheng Guo

Luminescence 2014 Volume 29( Issue 5) pp:540-548

Publication Date(Web):

DOI:10.1002/bio.2580

ABSTRACT

In this paper, 23 multi-aryl imidazole derivatives were synthesized and identified by nuclear magnetic resonance, ultraviolet-visible and elemental analysis. At the same time, their ultraviolet-visible maximum absorption (λ_ab^max), fluorescence emission maximum (λ_em^max) and quantum yields (Ф_f) were measured. The relationships between the optical behaviors and structures for these compounds were assessed. The results show that the λ^max_ab and λ^max_em are red-shifted and the fluorescence Ф_f are increased by the introduction of electron-withdrawing substituents and the increase in the planarity of multi-aryl imidazole molecules. The results also showed that the fluorescence quantum yields of the compounds containing two imidazole nuclei are double the corresponding mono-imidazole nucleus compounds. Copyright © 2013 John Wiley & Sons, Ltd.

Synthesis of phenacyl bromides via K2S2O8-mediated tandem hydroxybromination and oxidation of styrenes in water

Co-reporter:Qing Jiang, Wenbing Sheng and Cancheng Guo

Green Chemistry 2013 vol. 15(Issue 8) pp:2175-2179

Publication Date(Web):14 May 2013

DOI:10.1039/C3GC40515J

Non-transition metal-catalyzed synthesis of phenacyl bromides was achieved through K2S2O8-mediated tandem hydroxybromination and oxidation of styrenes. The advantages of this reaction are its excellent functional group compatibility, mild reaction conditions (60 °C) and use of pure water as reaction medium. Based upon experimental observations, a plausible reaction mechanism is proposed.

A Brønsted acid-catalyzed generation of palladium complexes: efficient head-to-tail dimerization of alkynes

Co-reporter:Tieqiao Chen, Cancheng Guo, Midori Goto and Li-Biao Han

Chemical Communications 2013 vol. 49(Issue 68) pp:7498-7500

Publication Date(Web):19 Jun 2013

DOI:10.1039/C3CC43131B

A Brønsted acid Ph2P(O)OH can efficiently catalyze the reaction of a Pd(0) complex with an alkyne to produce a novel alkenyl(alkynyl)palladium complex via selective hydropalladation and ligand exchange processes. On the basis of this finding, an efficient Pd(0)/Ph2P(O)OH mediated head-to-tail dimerization of alkynes was disclosed.

Cobalt(II)Porphyrin-Catalyzed Aerobic Oxidation: Oxidative Coupling of Phenols

Co-reporter:Qing Jiang;Wenbing Sheng;Mi Tian;Jie Tang ;Cancheng Guo

European Journal of Organic Chemistry 2013 Volume 2013( Issue 10) pp:1861-1866

Publication Date(Web):

DOI:10.1002/ejoc.201201595

Abstract

The first example of the cobalt–porphyrin-catalyzed aerobic oxidative coupling of phenols through oxidative C–H functionalization has been developed. In the presence of T(p-OMe)PPCo and Na₂CO₃, the oxidative coupling of phenols with different substituents proceeded smoothly with O₂ as a terminal oxidant to give the corresponding biaryl compounds in satisfactory yields. The biaryl derivatives are important in the area of pharmaceuticals and as ligands in metal catalysis. Preliminary mechanistic studies of this oxidative coupling reaction are also reported.

Substituent-induced regioselective hydroxylation of the aromatic CH bond on naphthalene with metachloroperbenzoic acid catalyzed by F20TPPMnCl

Co-reporter:Chang-Di Chen;Wen-Bing Sheng;Guo-Jun Shi

Journal of Physical Organic Chemistry 2013 Volume 26( Issue 1) pp:23-29

Publication Date(Web):

DOI:10.1002/poc.3012

The regioselective hydroxylation of the aromatic C–H bond on a series of naphthalenes with different β-substituent R (R = H, Me, Et, i-Pr, OMe, COOH, Br, etc.) was studied, and the substituent effect on the regioselectivity was investigated. The electron-donating substituent afforded the aromatic C–H bond hydroxylation at the 1α position with more than 80% selectivity, while the electron-withdrawing substituent afforded the aromatic C–H bond hydroxylation at the 4α position with more than 60% selectivity of β-substituted naphthalene hydroxylated with metachloroperbenzoic acid catalyzed by tetrakis(pentafluorophenyl)porphyrin manganese(III) chloride. The research showed that the steric and electronic effects of the substituent appeared to play a significant role in determining the regioselectivity, and the electronic effect was of more importance than the steric effect of the substituent in the current situation. The studies may provide additional proofs for the stepwise mechanism of the aromatic C–H bond hydroxylation through a cationic intermediate. Copyright © 2012 John Wiley & Sons, Ltd.

Phenyliodonium Diacetate Mediated Direct Synthesis of Benzonitriles from Styrenes through Oxidative Cleavage of C═C Bonds

Co-reporter:Jin-Hui Xu, Qing Jiang, and Can-Cheng Guo

The Journal of Organic Chemistry 2013 Volume 78(Issue 23) pp:11881-11886

Publication Date(Web):October 30, 2013

DOI:10.1021/jo401919h

A metal-free PhI(OAc)2 mediated nitrogenation of alkenes through C═C bond cleavage using inorganic ammonia salt as nitrogen source under mild conditions was developed, affording nitriles in moderate to good yields. The advantages of this reaction are mild reaction conditions, operational simplicity, and use of an ammonium salt as nitrogen source. Based upon experimental observations, a plausible reaction mechanism is proposed.

Oxidative Rearrangement of Internal Alkynes To Give One-Carbon-Shorter Ketones via Manganese Porphyrins Catalysis

Co-reporter:Wen-Bing Sheng, Qing Jiang, Wei-Ping Luo, and Can-Cheng Guo

The Journal of Organic Chemistry 2013 Volume 78(Issue 11) pp:5691-5693

Publication Date(Web):May 16, 2013

DOI:10.1021/jo400209p

Oxidative rearrangement of internal alkynes catalyzed by manganese(III) porphyrin is described, which opens a new access to one-carbon-shorter ketones using molecular oxygen. Under the standard conditions, a variety of alkynes including diarylalkynes and arylalkylalkynes rearranged smoothly to the corresponding ketones in high yields. Based upon experimental observations, a plausible reaction mechanism is proposed.

Remarkable effect of simple aliphatic alcohols on the controlled aerobic oxidation of toluene catalyzed by (T(p-Cl)PP)MnF/NHPI

Co-reporter:Wei Deng, Wei-Ping Luo, Ze Tan, Qiang Liu, Zhao-Min Liu, Can-Cheng Guo

Journal of Molecular Catalysis A: Chemical 2013 Volume 372() pp:84-89

Publication Date(Web):June 2013

DOI:10.1016/j.molcata.2013.02.012

The remarkable effect of simple aliphatic alcohols on the controlled oxidation of toluene with molecular oxygen over [5,10,15,20-tetrakis(p-chlorophenyl)porphinato]manganese fluoride (T(p-Cl)PPMnF) and N-hydroxyphthalimide (NHPI) was reported. The influences of reaction conditions such as the concentration and structure of alcohols, temperature and catalyst concentration on the promotion effect were also studied. UV–vis spectra were used to investigate the possible structure of reaction intermediate derived from the catalyst (T(p-Cl)PP)MnF in the toluene oxidation systems in the presence of methanol. The results showed that the added methanol interacted with catalyst (T(p-Cl)PP)MnF to form the coordination compound [(T(p-Cl)PP)MnIII(ROH)2]+, which subsequently was transformed into a high valent manganese-oxo radical cation intermediate [(T(p-Cl)PP)MnIV(O)(CH3OH)]+ in the oxidation systems. We deduce that the formation of [(T(p-Cl)PP)MnIV(O)(CH3OH)]+ and its higher reactivity toward toluene may be responsible for the better results observed. On the basis of the results obtained, a possible mechanism of the controlled oxidation of toluene with dioxygen over (T(p-Cl)PP)MnF/NHPI in the presence of the aliphatic alcohols was proposed.Graphical abstractHighlights► Toluene aerobic oxidation catalyzed by T(p-Cl)PPMnF/NHPI. ► Aliphatic alcohols markedly affect catalytic activity of T(p-Cl)PPMnF/NHPI. ► Controlled toluene oxidation to benzaldehyde and benzyl alcohol. ► Alcohols facilitate the formation of [(T(p-Cl)PP)MnIV(O)(CH3OH)]+.

Metalloporphyrin-catalyzed aerobic oxidation of 2-methoxy-4-methylphenol as a route to vanillin

Co-reporter:Qing Jiang, Wenbing Sheng, Xiangdong Guo, Jie Tang, Cancheng Guo

Journal of Molecular Catalysis A: Chemical 2013 Volume 373() pp:121-126

Publication Date(Web):July 2013

DOI:10.1016/j.molcata.2013.03.004

•Metalloporphyrins were effective for the aerobic oxidation of 2-methoxy-4-methylphenol.•Various reaction parameters were systematically investigated.•Catalysis under mild conditions.•A possible reaction mechanism was proposed.We report the use of simple metalloporphyrins (T(p-Cl)PPMnCl, T(p-Cl)PPCo, T(p-Cl)PPFeCl, T(p-Cl)PPCu or [T(p-Cl)PPFe]2O) as a catalyst for the direct oxidation of 2-methoxy-4-methylphenol to vanillin with molecular oxygen under mild conditions. The research results showed that the type of metalloporphyrin used, catalyst loading, temperature, reaction time, the amount of NaOH, solvent, the amount of solvent and the flow rate of oxygen influenced the conversion of 2-methoxy-4-methylphenol and the selectivity of vanillin. Under the optimal conditions, the conversion of 2-methoxy-4-methylphenol was up to 87% and the selectivity of vanillin reached 74%. A possible mechanism was also proposed for the present oxidation.

Theoretical studies and industrial applications of oxidative activation of inert C-H bond by metalloporphyrin-based biomimetic catalysis

Co-reporter:Qiang Liu;CanCheng Guo

Science China Chemistry 2012 Volume 55( Issue 10) pp:2036-2053

Publication Date(Web):2012 October

DOI:10.1007/s11426-012-4739-y

High costs and low catalytic efficiency of metalloporphyrins, which are an analogue of cytochrome P450 enzyme, are the bottlenecks in the industrialization of biomimetic hydrocarbon oxidation reactions. The basic principle and research technique of physical organic chemistry were applied to the process of biomimetic oxidation of hydrocarbon catalyzed by metalloporphyrins. This biomimetic technology could be adapted to bulk chemicals production by developing the new methods for efficient scale-up synthesis of metalloporphyrins, new pathways for molecular oxygen activation on an industrial scale and new approaches to elevate the catalytic efficiency of metalloporphyrins. This review mainly focuses on research carried out in our group.

New Group-Interaction Parameters of the UNIFAC Model: Aromatic Carboxyl Binaries

Co-reporter:Weiping Luo, Qinbo Wang, Liqun Fu, Wei Deng, Xiaoyong Zhang, and Cancheng Guo

Industrial & Engineering Chemistry Research 2011 Volume 50(Issue 7) pp:4099-4105

Publication Date(Web):March 1, 2011

DOI:10.1021/ie101934j

The solubility of p-toluic acid (PTA) in acetic acid (HOAc) + water solvent mixtures was measured by a static method. The experimental temperature ranged from 303.2 to 363.2 K, and the mole fraction of acetic acid in the solvent mixtures ranged from 0.546 to 1.000. Together with the available solid−liquid equilibrium (SLE) data for ternary systems of terephthalic acid (TPA) + HOAc + H2O and benzoic acid (BA) + HOAc + H2O, the interaction parameters of the new UNIFAC group ArCOOH, defined as an aromatic group (Ar) plus an (aromatic) carboxyl group (COOH), with an aliphatic carboxyl group (COOH), methyl group (CH3 and CH2), aromatic group (Ar), aromatic methyl group (ArCH3), and water are determined. By using the new defined group ArCOOH, the UNIFAC model predicted SLE data for the above three ternary systems agree with the experimentally determined results satisfactorily.

The preparation of terephthalic acid by solvent-free oxidation of p-xylene with air over T(p-Cl)PPMnCl and Co(OAc)2

Co-reporter:Yang Xiao, XiaoYan Zhang, Qin Bo Wang, Ze Tan, Can Cheng Guo, Wei Deng, Zhi Gang Liu, He Fei Zhang

Chinese Chemical Letters 2011 Volume 22(Issue 2) pp:135-138

Publication Date(Web):February 2011

DOI:10.1016/j.cclet.2010.09.027

An attempt has been made to prepare terephthalic acid (TPA) by solvent-free oxidation of p-xylene (PX) with air over tetra(p-chlorophenylporphinato)manganese chloride (T(p-Cl)PPMnCl) and cobalt acetate. The co-catalysis between T(p-Cl)PPMnCl and Co(OAc)2 has been discovered under solvent-free conditions. TPA yield could be increased significantly when T(p-Cl)PPMnCl and Co(OAc)2 were used together. The addition of T(p-Cl)PPMnCl into the reaction mixture over Co(OAc)2 significantly accelerated the rate-determining step of the oxidation process of PX to TPA. The effect of temperature on reaction was also investigated.

Effects of Oxygen Transfer Limitation and Kinetic Control on Biomimetic Catalytic Oxidation of Toluene

Co-reporter:Weiping LUO, Dawei LIU, Jun SUN, Wei DENG, Wenbing SHENG, Qiang LIU, Cancheng GUO

Chinese Journal of Chemical Engineering (May 2014) Volume 22(Issue 5) pp:509-515

Publication Date(Web):1 May 2014

DOI:10.1016/S1004-9541(14)60071-9

Under oxygen transfer limitation and kinetic control, liquid-phase catalytic oxidation of toluene over metalloporphyrin was studied. An improved technique of measuring dissolved oxygen levels for gas-liquid reaction at the elevated temperature and pressure was used to take the sequential data in the oxidation of toluene catalyzed by metalloporphyrin. By this technique the corresponding control step of toluene oxidation could be obtained by varying reaction conditions. When the partial pressure of oxygen in the feed is lower than or equal to 0.070 MPa at 463 K, the oxidation of toluene would be controlled by oxygen transfer, otherwise the reaction would be controlled by kinetics. The effects of both oxygen transfer and kinetic control on the toluene conversion and the selectivity of benzaldehyde and benzyl alcohol in biomimetic catalytic oxidation of toluene were systematically investigated. Three conclusions have been made from the experimental results. Firstly, under the oxygen transfer limitation the toluene conversion is lower than that under kinetic control at the same oxidation conditions. Secondly, under the oxygen transfer limitation the total selectivity of benzaldehyde and benzyl alcohol is lower than that under kinetic control with the same conversion of toluene. Finally, under the kinetics control the oxidation rate of toluene is zero-order with respect to oxygen. The experimental results are identical with the biomimetic catalytic mechanism of toluene oxidation over metalloporphyrins.

Transition metal-free C(sp3)–H bond coupling among three methyl groups

Co-reporter:Yufeng Liu, Xi Zhan, Pengyi Ji, Jingwen Xu, Qiang Liu, Weiping Luo, Tieqiao Chen and Cancheng Guo

Chemical Communications 2017 - vol. 53(Issue 38) pp:NaN5349-5349

Publication Date(Web):2017/04/19

DOI:10.1039/C7CC01309D

Copper-catalyzed aerobic conversion of the CO bond of ketones to a CN bond using ammonium salts as the nitrogen source

Co-reporter:Bin Xu, Qing Jiang, An Zhao, Jing Jia, Qiang Liu, Weiping Luo and Cancheng Guo

Chemical Communications 2015 - vol. 51(Issue 56) pp:NaN11267-11267

Publication Date(Web):2015/06/04

DOI:10.1039/C5CC02578H

A Brønsted acid-catalyzed generation of palladium complexes: efficient head-to-tail dimerization of alkynes

Co-reporter:Tieqiao Chen, Cancheng Guo, Midori Goto and Li-Biao Han